Molybdenum catalysts for the oxidation of unsaturated compounds in liquid phase

ABSTRACT

A molybdenum alkylene-dioxy-derivative, adapted to catalyze the oxidation of certain compounds containing ethylenic unsaturations, is prepared by reacting an organic molybdenum compound in which oxygen atoms are directly attached to the molybdenum atom with an organic derivative having vicinal hydroxyl groups.

nited States Patent Mattucci et a1.

[ 51 June 6,1972

[54] MOLYBDENUM CATALYSTS FOR THE OXIDATION OF UNSATURATED COMPOUNDS IN LIQUID PHASE [72]' Inventors: Anna Maria Mattucci, Torino; Emilio Perrotti, San Donato Milanese, both of Italy [73] Assignee: Snam Progetti S.p.A., Milan, Italy [22] Filed: Sept. 5, 1969 [21] Appl. No.: 855,739

[30] Foreign Application Priority Data Sept. 5, 1968 Italy ..20871 A/68 [52] U.S. Cl ..260/429 J, 260/3485 R [51] Int. Cl ...C07f 11/00, CO7d 1/08 [58] Field'of Search ..260/429 [56] I References Cited UNITED STATES PATENTS 2,795,552 6/1957 Abbottetal ..252/49.7 3,121,059 2/1964 DeYoungetal ..252/42.7

FOREIGN PATENTS OR APPLICATIONS OTHER PUBLICATIONS Flaschka et aL, Chelates in Analytical Chemistry, Marcel Dekker, Inc. New York, New York, 1967, pp. 274- 280. Richardson J. Inorg. Nucl. Chem, 1959, Vol. 9, pp. 273- 278 Larson et a1. Inorg. Chem. 1 (1962) pp. 856- 857 Price et al ..260/429 Germany Primary Examiner-James E. Poer Assistant Examiner-A. P. Demers Attorney-Ralph M. Watson [5 7] ABSTRACT 7 Claims, No Drawings MOLYBDENUM CATALYSTS FOR THE OXIDATION OF UNSATURATED COMPOUNDS IN LIQUID PHASE This invention relates to molybdenum derivatives suitable for use as catalysts in the oxidation of certain compounds containing ethylenic unsaturations.

According to one aspect of the present invention there is provided an organo-molybdenum compound represented by one of the following general formulas:

and

wherein each of R R R and R,,, which may be the same or different, is a hydrogen atom, an unsubstituted or substituted hydrocarbon radical having from one to carbon atoms, or a group having one of the formulas and -NQ where R is a hydrocarbon radical having from one to 10 carbon atoms, or where R and R and/or R and R may form a bivalent hydrocarbon radical.

The molybdenum compound of the present invention is suitable for use as a catalyst capable of catalyzing the oxygen transfer in a homogeneous phase from, for example, a peroxy compound of the type ROOH, wherein R alkyl, cycloalkyl, aryl, aralkyl or acyl, to an unsaturated compound of the type having the general formula:

wherein each of R R R and R,,, which may be the same or different, may be a hydrogen atom, an alkyl group having from one to eight carbon atoms, or an aryl, alkaryl, cycloalkyl, hydroxyalkyl or cyano-alkyl group, so as to give the corresponding epoxides.

The compounds of the present invention may also be employed in the synthesis of the hydroxy-hydroperoxides described and claimed in the specification of our co-pending application, Ser. No. 855,738, filed of even date herewith.

As oxidation catalysts the compounds of the present invention have an effectiveness regarding kinetics and yields, which is generally higher than known catalysts. The monomer type products (I) are colorless, whereas the dimer products (11) are yellow and identifiable in the IR. spectrum by a characteristic absorption at about 750 cm. which can be ascribed to the presence of the Mo-O-Mo group. The monomer products are identified by strong bands appearing as a triplet in the range idic compound with a loss of active oxygen. The extent of the radical type reaction depends upon the peroxide. This limits the use of the known catalysts to those cases in which this decomposition reaction may be considered negligible.

On the other hand, the molybdenum alkylene-dioxy-derivatives of the invention show no or substantially no catalytic activity towards radical-type reactions and, therefore, they are of wide application. The stability of the peroxides solutions in the presence of the molybdenum catalysts of the invention is a consequence of this.

The compounds of the present invention can all be obtained from a molybdenum compound in which oxygen atoms are directly attached to the molybdenum atom, e.g. molybdenum trioxide or from other molybdenum compounds, preferably organic compounds, by reaction with an organic derivative having vicinal hydroxyl groups, e.g. the vicinal alkylene glycols having from two to 12 carbon atoms in the molecule.

The products of the invention undergo prototropic phenomena and, therefore, the formulas I and II are not always correct as regards the position of the hydroxyl hydrogen.

When the diols contain at least one hydroxyl group of the tertiary type, the dimer (II) is directly obtained, but in other cases the monomer (l) is obtained. However each of the two types of product is transforrnable to the other, since the monomer (I) changes into the dimer (ll) by dissolving the monomer in benzene and distilling, as an azeotropic mixture, the water formed upon condensation to the dimer; and by treating a dimer (II) with water in benzene the corresponding monomer (l) forms.

The preparation reaction of the compounds according to the present invention generally takes place at temperatures of from 20 to+1 10 C., preferably from 30 to 70 C.

As solvents for the reaction, use can be made of the reagents themselves or hydrocarbon-type inert solvents, either alone or in admixture with higher alcohols.

The following examples illustrate the present invention.

EXAMPLE 1 This Example describes the preparation of a molybdenum alkylene-dioxy-derivative having the formula I], where R, R H, and R R =CH 12 g. of molybdenum acetylacetonate (W. Conard F ernelius, Kazuji Terada, and Burl E. Bryant, Inorganic Syntheses, 6, 147-148 (1960)) were dissolved in 20 g. of isobutylene glycol; the resulting solution was evaporated under vacuum to remove the excess glycol nearly to dryness; then 15 ml. of anhydrous benzene were added and the product was allowed to crystallize; it was filtered and washed with benzene. l l g. of a product were obtained, which, when subjected to elementary analysis, showed the following results:

Found Theoretical C 32.30 32.30 H 5.60 5.72 M.P. l07l 10 C.

EXAMPLE 2 This example describes the preparation of a molybdenum alkylene-dioxy-derivative of the formula ll type where R, R

880-920 cm." of the LR. spectrum, which bands can be correlated to the Mo 0 group.

When employing the usual known oxidation catalysts, there usually also occurs, besides the polar process of the oxygen transfer, radical-type decomposition processes of the perox- EXAMPLE 3 This example describes the preparation of a molybdenum alkylene-dioxy-derivative of the formula I type where R R =R =H, and R.,=CH

The preparation was similar to the preparation described in Example 2 except for the use of propylene glycol instead of isobutylene glycol.

Analysis of the product gave these results:

Found Theoretical C% 26.51 25.90 H% 4.89 5.08 M.P. l43 C.

EXAMPLE 4 Analysis:

Found C% 48.93 H7r 6.45 M.P. l88-l90 C., with decomposition.

EXAMPLE This Example describes the preparation of a molybdenum alkylcne-dioxy-derivative of the formula I type where and R R H.

12 g. of molybdenum acetylacetonate were completely dissolved with heating in 50 g. of racemic ethyl tanrate. Distillation was carried out under vacuum and 15 ml. of benzene and an excess of petroleum ether were added to the residue. 10 g. of a white crystalline product were crystallized. The product was analyzed as follows:

Found Theoretical C7z 35.30 35.68 H7( 4.9 4.83.

What we claim is: l. A process for preparing an organo-molybdenum compound reprcsented by one ofthe following general formulas:

and

wh erein each of R R R and R.,, which may be the same or different, is a hydrogen atom, an unsubstituted or substituted hydrocarbon radical having from one to 10 carbon atoms, or a group having one of the formulas COOR, CN, CONH and N0 where R is a hydrocar- V bon radical having from one to 10 carbon atoms, or where R and R and/or R and R; may form a bivalent hydrocarbon radical, which comprises reacting molybdenum acetylacetonate, with an organic derivative having vicinal hydroxyl groups so as to prepare the desired compound.

2. Process according to claim 1, wherein the organic derivative is a vicinal alkylene glycol having from two to 12 carbon atoms.

3. Process according to claim 1, wherein the reaction is carried out at a temperature in the range of from 20 to +1 10 C.

4. Process according to claim 3, wherein the reaction is carried out at a temperature in the range of from 30 to C.

5. Process according to claim 1, wherein the reaction is carried out in presence of a hydrocarbon solvent or a mixture of the same with a higher alcohol.

6. Process according to claim 1, wherein, when a compound of formula I is formed, it is dissolved in benzene and water is distilled off so as to fomi the corresponding compound of formula ll.

7. Process according to claim 1, wherein, when a compound of formula II is formed, it is treated with water and benzene so as to fonn the corresponding compound of formula I.

mg mm sums PATENT owxm ERTWECATE @F RREUN 3,668,227 June 6, 1972 Patent No. Dated Anna Maria Mattucci and Emilio Perrotti Inventofls) it is certified that mam-or oppoam in tho abovo-ifiomified patent and that said Lottero mum mm hex-ob wwocmd ma ohown below:

Colman 1, line 37, in the formula after C-R insert ,-co0R, --CN, oam-1 M line 72, inseit a double bond between "Mo" and "O" .1

Column 4, corr e ct formula "I" as follows:

)M E R3---C--0 \O--CR3 R4- I R4 Signed and sealed this 19th day of February 19714..

(SEAL) Attest: V 7 "NW.

EDWARD M.FLETCHER,JR. A H N Att sti o s Commlssloner of Patents 

2. Process according to claim 1, wherein the organic derivative is a vicinal alkylene glycol having from two to 12 carbon atoms.
 3. Process according to claim 1, wherein the reaction is carried out at a temperature in the range of from -20* to +110* C.
 4. Process according to claim 3, wherein the reaction is carried out at a temperature in the range of from 30* to 70* C.
 5. Process according to claim 1, wherein the reaction is carried out in presence of a hydrocarbon solvent or a mixture of the same with a higher alcohol.
 6. Process according to claim 1, wherein, when a compound of formula I is formed, it is dissolved in benzene and water is distilled off so as to form the corresponding compound of formula II.
 7. Process according to claim 1, wherein, when a compound of formula II is formed, it is treated with water and benzene so as to form the corresponding compound of formula I. 